EP1876268B1 - Procédé pour le dépot de chromium noir exempt de Cr-VI - Google Patents

Procédé pour le dépot de chromium noir exempt de Cr-VI Download PDF

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Publication number
EP1876268B1
EP1876268B1 EP06115347.4A EP06115347A EP1876268B1 EP 1876268 B1 EP1876268 B1 EP 1876268B1 EP 06115347 A EP06115347 A EP 06115347A EP 1876268 B1 EP1876268 B1 EP 1876268B1
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Prior art keywords
metallization
nickel
black chromium
prior
layer
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EP06115347.4A
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German (de)
English (en)
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EP1876268A1 (fr
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Wolf-Dieter Franz
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Priority to PCT/EP2007/055745 priority patent/WO2007144336A2/fr
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/37—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also hexavalent chromium compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • the present invention relates to a process for black chrome plating of surfaces, in particular for automotive interior surfaces.
  • Black chromium plating is a well-established and long-known method of surface coating in which, in addition to metallic chromium, more or fewer polychromates are deposited, depending on the morphology and the state of germination. It creates dark and especially black surfaces of decorative function. Black chromed surfaces generally suffer from limited abrasion resistance and also contain i. d. R. hexavalent chromium ions. Abrasion resistance varies depending on the application, but can be a significant disadvantage. The presence of hexavalent chromium is fundamentally disadvantageous because of the health hazard it poses and the environmental regulations prevailing, particularly in the automotive industry (eg RoHS compliance).
  • the EP 0 087 288 A discloses the treatment of black plating layers in phosphate baths.
  • the JP 54 095941 A according to the related Patent Abstract of Japan discloses rinsing chromate films on steel in pH 4-11 tap water, distilled water, deionized water or weakly alkaline solutions with ultrasound.
  • a method of producing a decorative black plating surface comprising the steps of: black plating a metallic surface, ultrasonically treating the chromium plated surface in an alkaline solution at a pH between 9 and 13.
  • the black chrome plating of metallic surfaces is conventional in itself.
  • the invention proposes an ultrasonic cleaning step after black chromium plating in an alkaline solution having a pH of between 9 and 13.
  • the black chrome plating requires a metallic surface, which in individual cases, for example, in metallic copper workpieces or stainless steel workpieces, even in an uncoated workpiece surface itself can exist.
  • an additional metallization preferably a galvanic metallization, is preferred.
  • nickel metallizations into consideration.
  • the cleaning step of the invention following the black chromium plating becomes efficient only through the combination of ultrasonication with the alkaline pH. It has surprisingly been found that both chemical cleaning and heat, such as cook-out, could not effectively reduce the Cr-VI loading of the black plating layer alone, but the use of ultrasound in alkaline setting provides quite significant advances. In this case, with the ultrasonic cleaning step, the Cr-VI load can be reduced to practically insignificant values, as can be verified in subsequent standard tests, such as by boiling with Diphenylcarbazidtest.
  • a cathodic activation of the metallized surface is preferably additionally provided before the black chrome plating.
  • a cathodic activation significantly improves the quality of the black chrome plating, above all it leads to a lower crack formation and thus supports the cleaning options by the ultrasonic cleaning step according to the invention.
  • the cathodic activation of the metallized surface before the black chromium plating also ensures a particularly efficient cleaning of the surface, also with regard to organic impurities remaining from previous metallization steps.
  • the cathodic activation provides a particularly fine-grained germination in the course of the following black chrome plating. This may be related to the reduction of particles on the surface by the cathodic circuit.
  • the layers according to the invention show a good and even improved abrasion resistance on the substrate compared to conventional layers and simultaneously a significantly reduced cracking of the black plating layer.
  • the initial metallization prior to cathodic activation is preferably a galvanic metallization, even in the case of materials other than nickel, such as in the case of copper.
  • a galvanic high-gloss nickel layer that is to say a nickel layer deposited from a galvanic bath with brightener additives.
  • metal is preferably first germinated, preferably with palladium. Germination may be preceded by a chemical pretreatment step, such as sulfonation or pickling in chromic acid solution.
  • the germination is followed by a chemical nickel coating, ie a nickel layer deposited without external current.
  • This nickel layer can then be galvanically reinforced, in particular with nickel or copper. Preference is given to pure galvanic nickel layers, ie without brightener additives in the electroplating bath, or copper layers of acidic electroplating solution, ie. H. based on sulfuric acid and not on cyanide.
  • the procedure according to the invention is also suitable for metal surfaces.
  • Particularly suitable metals are: non-ferrous metals, zinc die casting, light metals and light metal alloys, iron and steel materials.
  • An initially conventional layer structure is predefined on metal surfaces, for example with a galvanic metallization, in particular copper, and then a subsequent galvanic high-gloss metallization, in particular copper coating of acidic solution or nickel coating.
  • the high-gloss layers have the function of leveling the surface. The following procedure then continues as already explained in connection with the plastic surfaces; so it follows the cathodic activation.
  • the cathodic activation both on top as plastic coated original plastic surfaces so also metal surfaces, preferably takes place from an acidic solution, preferably at a pH between 1 and 2.
  • an acidic solution preferably at a pH between 1 and 2.
  • aqueous solutions based on sodium sulfate and sulfuric acid or on the Base of sodium hydrogen sulfate.
  • the solution may optionally also contain surfactants and / or fluorides.
  • surfactants and / or fluorides Preferably, amounts of about 30-100 g / l, more preferably 50-75 g / l sodium hydrogen sulfate.
  • a correspondingly converted amount of sodium sulfate can be dissolved and adjusted with sulfuric acid, the pH.
  • Preferred electrical parameters are 1 - 5 A / dm 2 at treatment times in the order of 10 - 300 s.
  • the voltage is adjusted to give the desired current density.
  • the cleaning step according to the invention after black chromium plating takes place in an alkaline solution in a pH range between 9 and 13, with pH values below 12 or below 11 being preferred, for example at pH 10.
  • the solution may optionally also contain surfactants. These improve the cleaning properties, but do not make the ultrasonic treatment unnecessary.
  • the ultrasonic treatment is carried out in a temperature range between 50 and 60 ° C.
  • the ultrasound treatment itself preferably lasts at least 30 s.
  • the ultrasound power can range between 0.5 and 2 W / l.
  • Another aspect of the invention relates to possibilities of adjusting the gloss or mattness of the black-chromed surface.
  • Here are to be created by fotomatten to high-gloss layers of play.
  • To set certain degrees of matting here is provided to produce the initial metallization of the surface by applying a matte nickel layer on a smooth surface of the workpiece by electrodeposition without organic matting additives and further applying a Sulfamatnickel Anlagen.
  • the basic idea of this aspect of the invention is to apply a matt nickel layer on a smooth workpiece surface and adjust the mattness over the thickness of the nickel layers. This is aimed at galvanic nickel layers, where no organic matting additives are used. Rather, in a preferred embodiment, it may be a known Wattsche nickel layer, which is technically simple and easy to control.
  • the smooth surface on the workpiece under the matt nickel layer may, for example, be a polished workpiece surface itself or else an applied metal layer. If a preferred bright nickel layer is used here, this has the particular advantage of very well leveling any surface defects and defects. Thus, it can improve the quality of the final gloss content of the finished metal surface according to the invention.
  • Galvanic processes for bright nickel coatings are well known and need not be detailed here. Commercial solutions are available, which may include, for example, nickel sulfate, organic brighteners, and so-called levelers. Suitable current densities in this range are 1 to 3 A / dm 2 . It may also be advantageous under the bright nickel layer already a shiny metal layer, such as a copper layer to provide.
  • the matte galvanic nickel layer is preferably applied as a known and technically well-controlled Wattsche nickel layer, ie as a galvanic nickel layer without organic matting additives.
  • Current strengths in the range of 0.1 to 2 A / dm 2 , better 0.1 to 1 A / dm 2 are preferred here.
  • the layer thickness of the matt layer should be comparatively low and may be between 0.05 and 5 .mu.m, with upper limits of 4 .mu.m, 3 .mu.m, 2 .mu.m and more preferably 1 .mu.m and lower limits of 0.075 .mu.m and more preferably 0.1 .mu.m even cheaper.
  • the layer thickness is ultimately determined by optical / aesthetic considerations.
  • the electrodeposition of a sulfamate nickel layer is also conventional and known.
  • the corresponding solutions contain nickel sulfamate, that is, the salt of amidosulfuric acid.
  • the sulfamate nickel coating rounds and reinforces the aforementioned nodular or otherwise matt nickel layer, but does not really level it.
  • the sulfamate nickel layer also enhances the grain size without changing fundamentals at the granularity referred to above as "nodular". It thus receives the matte character, possibly only slightly increases the gloss, but above all provides increased material strength for reasons of stability and resilience and for better wiping sensitivity or better dirt-repellent properties.
  • the roughness reduced by the rounding provides less grip to soiling.
  • a favorable thickness for the sulfamate nickel layer is in the range of 5 and 20 microns, with a lower limit of 10 and an upper limit of 15 microns are more preferred.
  • a particular advantage of this embodiment is that it can be set by galvanic parameters in a very simple manner, the degree of gloss or matte degree and even after the black chrome plating in the desired manner effect.
  • Different optical properties can be generated with one and the same basic process, that is, the same solution compositions, identical baths, etc. In particular, can be adjusted from batch to batch simply on the current, or even cheaper over the treatment time, the dullness. The thicker the matt nickel layer is, the higher the degree of matting results. This also applies after the application of the following black chrome layer.
  • a plastic door handle for automobiles made of glass-fiber or mineral fiber-reinforced polyamides, ABS or ABS-PC can be coated according to the invention by initially treating in the case of ABS and ABS PC a dressing with chromic acid or sulfonation in the case of polyamides.
  • a metal part namely an aluminum alloy automotive headrest support strut, first becomes electrolytically thick of 3 - 10 microns coppered. This is followed by an acidic high-gloss copper layer of thickness 20-25 ⁇ m and optionally another high-gloss nickel layer.
  • Both examples are then cathodically activated in an aqueous solution of 60 g / l sodium hydrogen sulfate at a pH of about 1.8, namely at 3 A / dm 2 for a time of 30 s.
  • the solution contains relatively small amounts of surfactants and fluorides to support the cleaning and activation function.
  • a black chromium plating layer known per se may be electrolytically deposited from a bath of about 450 g / l chromic acid, about 7.5 g / l chromium-III sulphate, of the order of 2-8 g / l sodium or Potassium carbonate or nitrate and about 1 g / l hexafluorosilicate.
  • This black plating layer has a thickness of about 0.3-2 ⁇ m.
  • Chromium VI oxides and polychromates are initially present on this layer. These impurities can be removed very successfully by a first simple water bath and then an ultrasound assisted cleaning in an alkaline solution at pH 10 and about 50-60 ° C for preferably at least 1-2 minutes. According to experience, treatments beyond 5 minutes do not bring any significant improvements. After the ultrasonic treatment in the alkaline solution again a water bath is run through.
  • the success of the invention can be controlled by a standard test by boiling with water and a diphenylcarbazide test of the cooking water. It can be z.
  • the method validated by Monosolmaschinentechnik ZVO ZVO-0101-UV-05
  • a test part is boiled under specified conditions and the Cr-VI content in the extraction solution according to DIN 38405 part 24 determined.
  • Cr-VI oxidizes 1,5-diphenylcarbazide to 1,5-diphenylcarbazone, which forms a violet-colored complex with the resulting Cr-III.
  • the absorbance of the dye at 540 nm is linearly related to the Cr-VI concentration, which can be evaluated by the calibration function or a comparative solution. With a standard test plate of 5 cm by 5 cm, it is allowed to boil out under the standard conditions for 10 minutes in 130 ml of water become. According to the invention, values below 300 ⁇ g / l Cr-VI can be achieved here.
  • an adjustable dullness in the manner already explained, follows the already mentioned galvanic high-gloss nickel layer of 15 to 25 microns, a matte Wattsche nickel layer. This is carried out at a current density of about 0.5 A / dm 2 from an aqueous solution containing 210 g / l nickel sulfate, 35 g / l nickel chloride and 40 g / l boric acid without further additives.
  • the preferred layer thickness range is between about 0.1 and 2 .mu.m, the mattness of the layer ultimately resulting being adjusted via the layer thickness. In this embodiment, 0.2 microns are deposited.
  • This layer thickness is meaningful only in terms of averaging.
  • the growth is very grainy or "bulbous", the individual grains are larger with increasing averaged layer thickness and have decreasing average distances. At significantly greater layer thicknesses, the grains are finally close, resulting in a matte layer that does not let the gloss of the underlying bright nickel layer through.
  • a sulfamate nickel layer is deposited on the Watt's nickel layer.
  • the grains are thereby reinforced, rounded the corners a bit and in particular the niches and angles lying on the edge of the grains filled.
  • a 12 ⁇ m thick layer is deposited at a galvanic current density of 1 A / dm 2 .
  • the aqueous solution contains 36% by volume of 60% by weight nickel sulphamate solution.
  • the galvanic solution contains 5 g / l nickel chloride and 35 g / l boric acid. Considered, for example, the bathroom Schlötter MS.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Physical Vapour Deposition (AREA)

Claims (15)

  1. Procédé de production d'une surface décorative présentant un chromage noir, comprenant les étapes consistant à :
    - réaliser le chromage noir d'une surface métallique,
    - nettoyer la surface à chromage noir dans une solution alcaline de pH compris entre 9 et 13 par traitement aux ultrasons.
  2. Procédé selon la revendication 1, dans lequel la surface est métallisée préalablement au chromage noir, notamment par nickelage.
  3. Procédé selon la revendication 2, dans lequel la métallisation de la surface préalablement au chromage noir consiste en une métallisation galvanique, notamment une métallisation galvanique à haut brillant.
  4. Procédé selon la revendication 2 ou 3, dans lequel la surface de départ consiste en une surface en matière plastique et la métallisation de la surface en matière plastique est précédée des étapes suivantes :
    - ensemencement avec un métal, notamment ensemencement avec du palladium,
    - nickelage chimique de la surface ensemencée,
    - renforcement de la couche de nickel par un apport galvanique de métal, notamment par nickelage mat ou cuivrage à partir d'une solution acide
  5. Procédé selon la revendication 4, dans lequel l'ensemencement avec un métal est précédé d'un traitement chimique préalable, notamment une sulfonation ou un mordançage à l'acide chromique.
  6. Procédé selon la revendication 1, 2 ou 3, dans lequel la surface de départ consiste en une surface métallique et la métallisation de la surface métallique est précédée des étapes suivantes :
    - métallisation galvanique, notamment cuivrage,
    - métallisation galvanique à haut brillant de la surface métallisée, notamment nickelage à haut brillant ou cuivrage à haut brillant à partir d'une solution acide.
  7. Procédé selon la revendication 6, dans lequel la surface métallique de départ est choisie dans le groupe constitué de : métaux non ferreux, alliage de zinc moulé sous pression, métaux légers et alliages de métaux légers, matériaux en fer et en acier.
  8. Procédé selon l'une des revendications précédentes comportant l'étape supplémentaire suivante :
    - activation cathodique de la surface métallisée préalablement au chromage noir.
  9. Procédé selon la revendication 8, dans lequel l'activation cathodique a lieu dans une solution acide, notamment à un pH compris entre 1 et 2.
  10. Procédé selon la revendication 9, dans lequel la solution acide contient essentiellement du sulfate de sodium et de l'acide sulfurique en solution aqueuse.
  11. Procédé selon la revendication 10, dans lequel la solution acide contient de 30 à 100 g/l d'hydrogénosulfate de sodium, ainsi éventuellement que des tensioactifs et éventuellement des fluorures.
  12. Procédé selon l'une des revendications 8 à 11, dans lequel l'activation cathodique s'effectue à une densité de courant allant de 1 à 5 A/dm2 pour 10 à 60 s.
  13. Procédé selon l'une des revendications précédentes, dans lequel l'étape terminale de nettoyage s'effectue dans la solution alcaline entre 50 et 60° C.
  14. Procédé selon l'une des revendications précédentes, dans lequel l'étape terminale de nettoyage s'effectue dans la solution aqueuse à une puissance ultrasonore de 0,5 à 2 W/l.
  15. Procédé selon l'une des revendications précédentes, dans lequel une surface interne d'automobile subit le chromage noir.
EP06115347.4A 2006-06-13 2006-06-13 Procédé pour le dépot de chromium noir exempt de Cr-VI Not-in-force EP1876268B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP06115347.4A EP1876268B1 (fr) 2006-06-13 2006-06-13 Procédé pour le dépot de chromium noir exempt de Cr-VI
PCT/EP2007/055745 WO2007144336A2 (fr) 2006-06-13 2007-06-12 Chromage noir dépourvu de cr-vi

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP06115347.4A EP1876268B1 (fr) 2006-06-13 2006-06-13 Procédé pour le dépot de chromium noir exempt de Cr-VI

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EP1876268A1 EP1876268A1 (fr) 2008-01-09
EP1876268B1 true EP1876268B1 (fr) 2013-05-15

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WO (1) WO2007144336A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3162919A1 (fr) 2015-10-29 2017-05-03 GmbH Franz Procédé de chromage noir efficace
EP3517655A1 (fr) 2018-01-25 2019-07-31 Franz GmbH Procédé de chromage noir
EP3564411A1 (fr) 2018-04-30 2019-11-06 Franz GmbH Procédé de chromage noir

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LT6119B (lt) 2013-05-30 2015-02-25 Valstybinio Moksliniå² Tyrimå² Instituto Fiziniå² Ir Technologijos Mokslå² Centras Juodo chromo dangų elektrolitinio nusodinimo būdas

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3162919A1 (fr) 2015-10-29 2017-05-03 GmbH Franz Procédé de chromage noir efficace
WO2017071817A1 (fr) 2015-10-29 2017-05-04 Franz GmbH Procédé efficace de chromage noir i
EP3312307A1 (fr) 2015-10-29 2018-04-25 Franz GmbH Procédé de chromage noir efficace
EP3517655A1 (fr) 2018-01-25 2019-07-31 Franz GmbH Procédé de chromage noir
EP3564411A1 (fr) 2018-04-30 2019-11-06 Franz GmbH Procédé de chromage noir

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